Bis-(n-acylamino-phthalimide)-disazo dyestuffs

ABSTRACT

SULFONIC ACID GROUP-FREE DISAZO DYESTUFFS ARE PREPARED WHICH ARE VALUABLE PIGMENT DYESTUFFS CHARACTERIZED BY GOOD FASTNESS TO LIGHT, SOLVENTS AND MIGRATION, AND BY A GOOD THERMAL RESISTANCE WHEN USED FOR COLORING PAPERS, LACQUERS, VARNISHES AND SYNTHETIC MATERIALS AND FOR THE PRODUCTION OF PIGMENT PASTE AND PRINTING INKS. THE DYESTUFFS CORRESPOND TO THE GENERAL FORMULA   1,3-DI(O=),2-(A-C(=X)-NH-),(R)M,((1,3-DI(O=),2-(A-C(=X)-   NH-),(R)M-ISOINDOLINYL)-N=N-K-N=N-)ISOINDOLINE   WHEREIN A STANDS FOR AN OPTIONALLY SUBSTITUED ALKYL, ARALKYL, CARBOCYCLIC OR HETEROCYCLIC RADICAL OR FOR THE RADICAL   -N(-R1)-R2   WHERE R1 AND R2 INDEPENDENTLY OF ONE ANOTHER, REPRESENT HYDROGEN, AN OPTIONALLY SUBSTITUTED ALKYL, ARALKYL OR ARYL RADICAL; X STANDS FOR AN OXYGEN OR SULFUR ATOM OR FOR NH; K STANDS FOR THE RADICAL OF A FIBUNCTIONAL COUPLING COMPONENT; R STANDS FOR A SUBSTITUENT; AND M IS AN INTEGER FROM O TO 3.

United States Patent 3,634,388 BIS-(N-ACYLAMINO-PHTHALIMIDE)-DISAZO DYESTUFFS Walter Horstrnann, Cologne, Dietmar Kalz, Leverkusen,

Gerhard Wolfram, Opladen, and Edgar Siege], Leverkusen, Germany, assignors to Farbenfabriken Bayer AG, Leverkusen, Germany No Drawing. Filed Nov. 26, 1968, Ser. No. 779,239 Claims priority, application Germany, Dec. 6, 1967, P 16 44 238.9 Int. Cl. C09b 33/02 US. Cl. 260-152 2 Claims ABSTRACT OF THE DISCLOSURE Sulfonic acid group-free disazo dyestuffs are prepared which are valuable pigment dyestuffs characterized by good fastness to light, solvents and migration, and by a good thermal resistance when used for coloring papers, lacquers, varnishes and synthetic materials and for the production of pigment paste and printing inks. The dyestuffs correspond to the general formula where R and R independently of one another, represent hydrogen, an optionally substituted alkyl, aral-kyl or aryl radical; X stands for an oxygen or sulfur atom or for NH; K stands for the radical of a bifunctional coupling component; R stands for a substituent; and m is an integer from 0 t0 3.

The object of the present invention relates to valuable new snlphonic acid group-free disazo dyestuffs of the general formula and to a process for their production.

In Formula I A stands for an optionally substituted alkyl, aralkyl, carbocyclic or heterocyclic radical or for the radical where R and R independently of one another, represent hydrogen, an optionally substituted alkyl, aralkyl or aryl radical, X stands for an oxygen or sulphur atom or for NH, K stands for the radical of a bifunctional coupling component, R stands for a substituent, and m is an integer from 0-3.

Suitable alkyl radicals A are, for example, branched and unbranched C -C alkyl radicals, such as methyl, ethyl, propyl, isopropyl or butyl radicals.

3,634,388 Patented Jan. 11, 1972 "ice Suitable aralkyl radicals are especially benzyl radicals,

such as Suitable carbocyclic radicals are especially optionally substituted aryl radicals, particularly phenyl radicals or 0 naphthyl radicals, such as or cycloalkyl radicals, such as cyclohexyl radicals.

Suitable heterocyclic radicals are, for example,

and suitable radicals are, for example, NH -NHC H -NHC H and Substituents R to be especially mentioned are alkyl groups, such as methyl, ethyl and butyl groups; halogen atoms, such as fluorine, chlorine and bromine; alkoxy groups, such as methoxy and ethoxy groups; nitro groups and trifiuoromethyl groups.

Suitable radicals K-- are, for example, the radicals of N,N' arylene bis-[2-hydroxynaphthoyl-(3-)-amides, N,N'-arylene-bis-acetoacetylamides, arylene bis-[3-methyl-pyrazolon-(5)-yles-(1)] and arylene-bis-[3-methyl-5- amino-pyrazoles-(l)] of the formula NHz NH? N-arylcne-N H d H The new disazo dyestuffs of the Formula I are obtained by reacting disazo compounds of the formula )m (II) in which K, R and m have the same meaning as above,

COOH

or their functional derivatives, for example dianhydrides, semiesters or neutral esters, in a molar ratio 1:2 in highboiling organic solvents, optionally in the presence of condensing agents, with compounds of the formula in which A and X have the same meaning as above, and selecting the starting components free from sulphonic acid groups.

One group of particularly valuable dyestuffs Within the range of the dyestuffs of the Formula I is obtained by reacting disazo dyestuffs of the formula HOOC -COOH HOOC- COOH (R)m (11), (IV) in which K, R and m have the same meaning as above,

or their dianhydrides, semiesters or neutral esters with compounds of the Formula III which yield disazo dyestuffs of the formula Especially preferred dyestuffs are those of the formula where X is selected from the group consisting of O, S, and NH;

121 is an integer from O to 3;

R is selected from the group consisting of alkyl with 1-4 carbon atoms, fluorine, chlorine, bromine, methoxy, ethoxy, nitro and trifluoromethyl;

A is selected from the group consisting of alkyl with 1-8 carbon atoms; cyclohexyl; phenyl; phenyl substituted by a member Cl, CH CONH or NHOCCH benzyl, benzyl substituted by a member C1, CH or OCH naphthyl, pyridyl; carbanilino phenylene; carbanilino phenylene substituted by a member C1 or CH benzoylamino phenylene; benzoylamino phenylene substitued by a member Cl or CH or A is a radical where R and R are selected from the group consisting of H; methyl, ethyl and phenyl; and

K is selected from the group consisting of N,N-arylenebis[2'-hydroxy-naphthoyl(3-)-amide], N,N' arylenebis[acetoacetylamide], N,N arylene-bis[S-methyl-pyrazolone(5)yle(1) N,N-arylene-bis[3-methyl-5-amino-pyrazole(1)], where arylene is a bivalent radical selected from the group consisting of where L is CH 0, CH CH, NHCONH; and R is H, C1 or CH The starting dyestuffs of the Formula II or their functional derivatives are obtained in conventional manner by diazotising the optionally substituted aminophthalic acids or their functional derivatives and coupling with bifunctional coupling components. The following diazo components may be used for this purpose, for example:

3- and 4-aminophthalic acid, 3-amino-phthalic acid dimethyl ester, 3-amino-6-methyl-phthalic acid, 3-amino-5-nitro-phthalic acid, 3-amino-6-methoxy-phthalic acid, 3-amino-4-methoxy-phthalic acid, 3-amino-6-chloro-phthalic acid, 3-amino-5,6-dimethoxy-phthalic acid, 4-amino-3-chloro-phthalic acid, 4-amino-S-chloro-phthalic acid, 4-amino-phthalic acid dimethyl ester, 4-amino-3-methyl-phthalic acid, 4-amino-5-methyl-phthalic acid, 4-amino-3-methoxy-phthalic acid, 4-amino-S-methoxy-phthalic acid and 4-amino-3,6-dichloro-phthalic acid.

As bifunctional coupling components H-K-H there may be used, for example:

N,N-bis-( 3 '-hydroxy-naphthoyl- (2) )-4",4"'-diaminodiphenyl-urea,

N,N'-bis- (acetoacetyl) -phenylene-diamine-1,4,

N,N-bis- (acetoacetyl -2,5-dichlorophenylenediaminel ,4,

N,N-bis- (acetoacetyl) -2,5-dimethyl-phenylenediamine-1,4,

N,N'-bisacetoacetyl) -2-chloro-phenylenediamine-1,4,

N,N-bisacetoacetyl) -2-methyl-phenylenediamine-l ,4,

N,N'-bisacetoacetylamine -biphenylene-4,4,

N,N'bis- (acetoacetylamino -3,3 -dimethyl-biphenylene-4,4',

N,N-bisacetoacetylamino -2,2-dichloro-biphenylene-4,4,

N,N-bis- (acetoacetylamino 3 ,3 '-dichloro-biphenylcue-4,4,

N,N'-bis acetoacetyl -4,4'-diamino-diphenylmethanephenylene- 1 ,4-bis- (3 '-methyl-pyrazolone- 5 -yl-( 1) phenylene- 1,4-bis- (3 '-methy1-5'-amino-pyrazoly1-( 1 biphenylene-4,4'-bis-( 3 "-methyl-S-amino-pyrazolylbiphenylene-4,4'-bis- (3 "-methyl-pyrazolon- (5 (3 ,3 -dimethyl-biphenylene- 4,4) -bis- 3 "-methylpyrazolon- (5" -yl-( 1") (3,3 -dimethyl-biphenylene-(4,4') )-bis (-3 "-methyl-S amino-pyrozolyl-( 1") Compounds (III) suitable for the production of azo dyestuffs of the Formula I are, for example: semicarbazide, thiosernicarbazide, aminoguanidine and their substitution products, e.g.

4-methylsemicarbazide,

4-phenylsemicarbazide,

4-benzylsemicarbazide,

4-cyclohexylsemicarbazide, 4,4-dimethylsemicarbazide, 4-methyl-thiosemicarbazide, 4-phenyl-thiosemicarbazide, 4-benzylthiosemicarbazide, 4-cyclohexylthiosemicarbazide, 4,4-dimethylthiosemicarbazide, N-amino-N-methyl-guanidine, N-amino-N-phenyl-guanidine, N-amino-N'-cyclohexyl-guanidine, or N-acetylhydrazine,

propionic acid hydrazide,

phenyl-acetic acid hydrazide,

4-chloro-phenyl acetic acid hydrazide,

benzoic acid hydrazide,

4-chloro-benzoic acid hydrazide, 3,4-dichloro-benzoic acid hydrazide, 4-methyl-benzoic acid hydrazide, 4-methoxy-benzoic acid hydrazide, 4-carbanilino-benzoic acid hydrazide,

4- (4-chloro-carbanilinq) -benzoic acid hydrazide 4-(3',4-dichloro-carbanilino)-benzoic acid hydrazide, 4-(2',4', -trichloro-carbanilino)-benzoic acid hydrazide, 4-(4'-methyl-carbanilino)-benzoic acid hydrazide, 4-carbarnido-benzoic acid hydrazide, cyclohexane-carboxylic acid hydrazide,

naphthoic acid-Z-hydrazide,

naphthoic acid-l-hydrazide,

nicotinic acid-hydrazide,

isonicotinic acid hydrazide, 4-(2,5'-dichloro-carbanilino)-benzoic acid hydrazide, 4-acetylamino-benzoic acid hydrazide, 4-benz0yl-amino-benzoic acid hydrazide, 4-(4'-chloro-benz0ylamino)-benzoic acid hydrazide, 4-(4-methyl-benzoylamino) -benzoic acid hydrazide, 2,5-dichloro-4-carbamido-benzoic acid hydrazide, 3-carboxamido-benzoic acid hydrazide, 3-carboxamido-4-chloro-benzoic acid hydrazide.

Organic solvents suitable for the condensation of the monoazo dyestuff (II) or (IV), or their derivatives with the compounds (III) are the following solvents which boil above C., for example: benzene, toluene, xylenes, chlorobenzene, 0-, m-, p-dichlorobenzene, trichlorobenzenes, quinoline, nitrobenzene, glacial acetic acid, cyclohexane, 1,2,3,4 tetrahydro-naphthalene, naphthalene, tetrachloroethylene, anisole, diphenyl ether, di-n-butyl ether, Decalin, and mixtures of such solvents. Preferred condensing agents which are concurrently to be used are, for example: acidic, water-eliminating agents, such as formic acid, acetic acid, propionic acid, anhydrous sodium acetate, zinc chloride, iron(III) chloride, aluminum chloride and boron trifluoride.

The reaction of (II) or of the corresponding dianhydrides, semiesters or esters with the compounds (III) is performed in a molar ratio of about 1:2. In general, the operation is carried out with an excess of 1020% of the component (III) in order to achieve a reaction of (II) as complete as possible. Dependent upon the use of idenitical or diiferent compounds (III), symmetric or asymmetric dyestuffs of the Formula I are obtained.

The products obtainable according to the present process are valuable new pigment dyestulfs which are generally characterised by good fastness to light, to solvents and to migration as well as by a good heat resistance in the various substrates. They are used for the colouring of paper, lacquers and synthetic materials, such as, e.g., plasticiser-containing polyvinyl chloride, polyethylene and acrylonitrile/butadiene/styrene coand graft-polymers, and for the production of pigment pastes and printing inks.

The parts in the following examples are parts by weight, the temperatures are given in degrees centigrade.

EXAMPLE 1 7 parts of the disazo dyestulfs obtained from 2 mol diazotised 3-amino-phthalic acid and 1 mol N,N-bis (acetoacetyl)-2,5-dichloro phenylene diamine-1,4 and 3.2 parts cyclohexane carboxylic acid hydrazide are heated at 120 for 4 hours in a mixture of 225 parts 0- dichlorobenzene and 25 parts glacial acetic acid; the barely soluble pigment is filtered off with suction while hot, washed with 200 ml. hot o-dichlorobenzene and ml. benzene and dried at 50 in a vacuum. 7.5 parts of a lightfast, greenish yellow pigment dyestuif of the formula C OCH:

are obtained.

EXAMPLE 2 8.3 parts of the disazo dyestuif obtained from diazotised 3-aminophthalic acid and N,N'-bis-[2-hydroxynaphthoyl- (3)-amino]-phenylene-1,4 are heated at -120 for 2 hours in a mixture of 200 parts o-dichlorobenzene and 20 parts glacial acetic acid; 6 parts 3,4-dichloro-benzoic acid hydrazide are then added and the mixture is kept at for 10 hours, the product is then filtered OE With suction while hot, washed with 200 ml. hot o-dichlorobenzene and dried in a vacuum until the weight is constant. The yield amounts to 11 parts of a red pigment dyestuff of the formula When the procedure given in the above examples is R is selected from the group consisting of alkyl with 1-4 followed but, instead of the diazo, coupling and imidation carbon atoms, fluorine, chlorine, bromine, methoxy, components (III), those set out in the following table are 15 ethoxy, nitro and trifiuoromethyl; used, valuable pigment dyestuffs with the specified shades A is selected from the group consisting of alkyl with 1-8 are likewise obtained. carbon atoms; cyclohexyl; phenyl; phenyl substituted by Diazo component Coupling component Imidation component Shade S-amino-phthalic acid N ,N-bis-[2hydroxy-napl1thoyl-(3)]-pl1enylcne- Semicarbazide Red,

diaminel,4. Do. "do." Thiosemiearbazide Red. .do Aminoguanidine Red. do c 4-chloro-bcuzoic aci -hydrazide Red.

"do. 4-(4-chloro-earbanilino)-benz0ic acid hydrazrdm Red.

"do." Cyclohexaue-carboxylic-aeid-hydrazide. Red.

Do. N,N-bis-[2-hydroxy-naphthoyl-(3)]-2-cl1l0ro- Scmiearbazide Red.

phenylene-diamiue-l,4.

Thlosemicarbazide. Red.

4-(4-chloro-earbanilino)-benz0ic acid-hydrazidml Red. Cyclohexane-carboxylic acid-hydrazide. R

Thioscmicarbazide Red.

l-chloro-bcnzolc acid-hydrazide Red.

4-carbanilino-benzoic acid-hydrazide Semicarbazide 4-carboxamid0-benzoic acid H2 ,4 ,5 ,-triehl0r0-carbanllino) -benz0ic ac hydrazide. Do. N,N-bis-[2-hydr0xy-naphthoyl-(3)]-phenylcne- Semicarbazide Red.

diamiue-1,4.

4-benzoylamino-benzoic aeid-hydrazide. Red Do. (10 4-(4-ehloro-carbanilino)-benzoic acid-l1ydrazidc Red. S-amino-phthalic acid. N,N-bis-(acet0acetyl)-2,fi-dichloro-phenylene- Scmicarbazidc Yellow.

(Ermine-1,4.

Thiosemicarbazide.. Do. Amino-guauidine.... D0. 2-chloro-benzoic acid hydrazide- Do. -methyl-beuzoic acid-hydrazidc... D0. 4-carbanilin0-bcnz0ic acid-hydrazide D0. 2-aeetylamino-benzoic acid-hydrazide. D0. Semicarbazide D0. 4chl0ro-benzoic acid-hydrazide D0. 4carboxamldo-benzoic aeid-hydraz D0. 4(4-cl1loro-carbanilino)-benzoic acid-l1 D0. y unethyl-phcnylene- Semicarbazidc D0.

Cyclohcxaue-carboxylic acidhydrazide Do. 2-elrloro-beuzoic acid-hydrazidc. D0. 4-mcthyl-beuz0ic acid-hydrazide Do. (I 4-carboxamid0-bcnzoic acid-hydrazide. 'Do. ])0 N ,N-b1s (acet0acetyl)-2-rnetliy1-5-cl1l0r0-phenyl- Sernicarbazade D0,

euc-diamine-L4.

-cllloro-beuzoic acid-hydrazide. D0. 4-methyl benzoic acid-hydrazide Do. Cyclohexane-carboxylic acid-hydrazide Do. yl-pyrazolon-(5)- Semicarbazide D0.

Cyclohexaneearboxylic acid-hydrazidc Do. 4chl0r0-benz0ic acid-hydrazide Do. I) d 4-carboxamido-benzoic acid-hydrazide. Do. 4-a1nin0-5-n1e l l y-pi 1alicacid N,N-b a y Scmicarbazide Red.

diamine-l,4. Do d0 4-cl1loro-beuzoic acid-hydrazide D0. D0 N,N-bis-(aeetoacctyl)-2,S-dichloro-phenylene- Cyclohexane-carboxylic acid-hydrazide Yellow.

diamine-l,4 D0. do 4-earbanilin0-benzoic acid-hydrazide Do.

We claim: a member Cl, CH CONH or NHOCCH benzyl, 1. Sulfomc acid group-free dlsazo dyestuffs of the benzyl substituted by a member Cl, CH or OCH formula naphthyl, pyrrdyl; carbanilrno phenylene; carbanihno 0 0 G9 phenylene substltuted by a member C1 or CH benzoyl- II II amino phenylene; benzoylamrno phenylene substltuted C by a member C1 or CH or AC-NH-N N=N1-N=N N-NH-C-A A 15 a fadlcal I R f m ll (mm (B m 0 0 R2 where: X is selected from the group consistmg of O, S, and NH; Where R and R are selected from the group consisting in is an integer from 0 to 3; 75 of H; methyl, ethyl and phenyl; and

10 K is selected from the group consisting of N,N'-arylene- 2. Sulphonic acid group-free disazo dyestuffs of claim bis[2'-hydroxy-naphthoyl-(3') amide], N,N-arylene- 1 of the formula bis[acetoacetyl-a'mide], N,N-arylene bis[3 methyl- 0 pyrazolone )yle(1)], N,N'-arylene bis[3 methyl- I I II 5-amino-pyrazo1e(1)], where arylene is a bivalent radi- 5 X X cal selected from the group consisting of g (R)m (R)m (I) Q References Cited 3' FOREIGN PATENTS 6,701,983 9/1967 Netherlands 260-452 R R HENRY R. JILES, Primary Examiner D. M. PAPUGA, Assistant Examiner Where L is H2, 0, CH=CH, NHCONH; and R' is H, 01 or CH3. 106-22, 22s; 117 13s.s, 154;260-156, 

